铜铟镓硒薄膜的氧化物墨水法制备与性能研究
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摘要
薄膜太阳能电池在国民经济和国防科技的各个领域具有广泛地应用。铜铟镓硒(CIGS)薄膜太阳能电池具有成本低、光电转换效率高和性能稳定等优点,成为国内外研究的热点。而在CIGS薄膜太阳能电池中,CIGS吸收层是关系到电池转换效率的关键。本论文主要对非真空先驱体墨水法制备CIGS吸收层进行了详细地研究和探讨,并对吸收层的性能进行了测试。
论文首先以铜、铟和镓的硝酸盐为原料,经共沉淀和高温煅烧工艺制备出纳米金属氧化物。综合考虑粒径与团聚等因素,较优沉淀条件为:体系pH值控制为8.0,沉淀温度为50℃;较优煅烧条件为:煅烧温度550℃,恒温时间为10h。所制备金属氧化物的粒径约80nm,比表面积为48.8m2/g,其组成主要为氧化铜、氧化铟和氧化镓的混合物,其中Cu/(In+Ga)比为1.03,Ga/(In+Ga)比为0.16。
将纳米金属氧化物、分散剂Orotan1124和水按一定的质量配比混合后经高能球磨制备出氧化物墨水,然后采用自流平方式在不锈钢基底上涂覆成膜。结果表明,造成氧化物墨水不稳定的主要因素是颗粒间的团聚。提高墨水中颗粒分散稳定性,一是减小颗粒的粒径大小,二是增强颗粒之间的静电作用力。
氧化物薄膜经退火处理后,在氢气气氛中经高温还原处理得到铜铟镓(CIG)合金薄膜。结果表明,还原温度是影响合金薄膜组成和形貌的关键因素:当还原温度高于550℃时,合金薄膜中形成大量球状颗粒。较优的还原条件为:还原温度为500℃,还原时间为60min。铜铟镓合金薄膜主要由Cu11In9、Cu9In4、In2O3、Cu等组成,其Cu/(In+Ga)比为0.98,Ga/(In+Ga)比为0.16。
将铜铟镓合金置于真空条件下采用固体源后硒化法进行硒化处理制备CIGS吸收层。较优的硒化条件为:250℃恒温30 min,550℃恒温40 min。XRD分析及元素分析表明,产物为黄铜矿结构的CuIn1-xGaxSe2多晶薄膜。薄膜中Cu/(In+Ga)比为0.92,Ga/(In+Ga)比为0.14,Se/(Cu+In+Ga)比为0.92。
霍尔效应测试表明CIGS薄膜为p型半导体,其载流子浓度为4.5×1014/cm3,迁移率为217cm2/V·s,电阻率为63Ω·cm;光谱测试表明CIGS薄膜的带隙宽度高于1.1eV,可用于太阳能电池的制备。
Thin-film solar cells are playing an important role in national economy and national defense technology. CuIn1-XGaXSe2 (CIGS) thin-film solar cells are thought to be the most promising solar cells because of its low cost, high efficiency, and stabilization. CIGS thin film is the most important structure in CIGS solar cells, which decides the conversion efficiency of the thin-film solar cells. In this paper, the fabrication of CIGS thin film using non-vacuum nanoparticle precursor inks was investigated. The properties of CIGS thin film were characterized.
Nanoparticles of Cu, In and Ga oxides were prepared by co-precipitation and calcination using Cu(NO3)2, In(NO3)3 and Ga(NO3)3 as raw materials. Considering the particle size and aggregation of oxides, the optimal precipitation conditions were that pH was about 8. and the temperature was about 50℃. The optimal calcining conditions were that the temperature was about 550℃and the holding time was about 10 hours. The mean particle size of metal-oxides was about 80 nm. The average surface area was about 48.8 m2/g. It was the mixture of CuO, In2O3 and Ga2O3. The Cu/(In+Ga) ratio was 1.03, the Ga/(In+Ga) ratio was 0.16.
The ink was prepared by milling of the oxides mixture, a dispersing agent (Orotan 1124) and water. The ink was coated on the stainless steel to form the oxides film. The results indicated that the aggregation of nanoparticles was the major factor in the unstableness of the ink. The stabilization of the ink can be improved by reducing the size of the particle and enhancing electrostatic force of nanoparticles.
After it was annealed in air, the oxides film was reduced in H2 gas in order to form Cu-In-Ga (CIG) alloys film. The results revealed that the temperature of reduction was the most important effects on the morphology and composition of alloys film. When the temperature was higher than 550℃, there appeared many spherical particles on the alloys film. The optimal conditions of reduction were that the temperature was 500℃and the time was 60 minutes. The alloys consisted of Cu11In9, Cu9In4, In2O3 and Cu. The Cu/(In+Ga) ratio was 0.98, the Ga/(In+Ga) ratio was 0.16.
The CIGS film was obtained by the selenizing of Cu-In-Ga alloys using solid Se as raw materials in vacuum. The optimal conditions of selenization were that the first stage was at 250℃for 30 minutes, the second stage was at 550℃for 40 minutes. The XRD and EDS results showed that the production was polycrystalline CuIn1-xGaxSe2. The Cu/(In+Ga) ratio was 0.92, the Ga/(In+Ga) ratio was 0.14, the Se/(Cu+In+Ga) ratio was 0.92.
The reslut of hall effect measurement showed that the CIGS film was p-type semiconductor. The carrier concentration, mobility and the resistivity of CIGS film were about 4.5×1014/cm3, 217cm2/V·s and 63Ω·cm, respectively. The spectrum analysis indicated that the band-gap of the CIGS film was higher than 1.1eV, which can be used in the solar cells.
论文首先以铜、铟和镓的硝酸盐为原料,经共沉淀和高温煅烧工艺制备出纳米金属氧化物。综合考虑粒径与团聚等因素,较优沉淀条件为:体系pH值控制为8.0,沉淀温度为50℃;较优煅烧条件为:煅烧温度550℃,恒温时间为10h。所制备金属氧化物的粒径约80nm,比表面积为48.8m2/g,其组成主要为氧化铜、氧化铟和氧化镓的混合物,其中Cu/(In+Ga)比为1.03,Ga/(In+Ga)比为0.16。
将纳米金属氧化物、分散剂Orotan1124和水按一定的质量配比混合后经高能球磨制备出氧化物墨水,然后采用自流平方式在不锈钢基底上涂覆成膜。结果表明,造成氧化物墨水不稳定的主要因素是颗粒间的团聚。提高墨水中颗粒分散稳定性,一是减小颗粒的粒径大小,二是增强颗粒之间的静电作用力。
氧化物薄膜经退火处理后,在氢气气氛中经高温还原处理得到铜铟镓(CIG)合金薄膜。结果表明,还原温度是影响合金薄膜组成和形貌的关键因素:当还原温度高于550℃时,合金薄膜中形成大量球状颗粒。较优的还原条件为:还原温度为500℃,还原时间为60min。铜铟镓合金薄膜主要由Cu11In9、Cu9In4、In2O3、Cu等组成,其Cu/(In+Ga)比为0.98,Ga/(In+Ga)比为0.16。
将铜铟镓合金置于真空条件下采用固体源后硒化法进行硒化处理制备CIGS吸收层。较优的硒化条件为:250℃恒温30 min,550℃恒温40 min。XRD分析及元素分析表明,产物为黄铜矿结构的CuIn1-xGaxSe2多晶薄膜。薄膜中Cu/(In+Ga)比为0.92,Ga/(In+Ga)比为0.14,Se/(Cu+In+Ga)比为0.92。
霍尔效应测试表明CIGS薄膜为p型半导体,其载流子浓度为4.5×1014/cm3,迁移率为217cm2/V·s,电阻率为63Ω·cm;光谱测试表明CIGS薄膜的带隙宽度高于1.1eV,可用于太阳能电池的制备。
Thin-film solar cells are playing an important role in national economy and national defense technology. CuIn1-XGaXSe2 (CIGS) thin-film solar cells are thought to be the most promising solar cells because of its low cost, high efficiency, and stabilization. CIGS thin film is the most important structure in CIGS solar cells, which decides the conversion efficiency of the thin-film solar cells. In this paper, the fabrication of CIGS thin film using non-vacuum nanoparticle precursor inks was investigated. The properties of CIGS thin film were characterized.
Nanoparticles of Cu, In and Ga oxides were prepared by co-precipitation and calcination using Cu(NO3)2, In(NO3)3 and Ga(NO3)3 as raw materials. Considering the particle size and aggregation of oxides, the optimal precipitation conditions were that pH was about 8. and the temperature was about 50℃. The optimal calcining conditions were that the temperature was about 550℃and the holding time was about 10 hours. The mean particle size of metal-oxides was about 80 nm. The average surface area was about 48.8 m2/g. It was the mixture of CuO, In2O3 and Ga2O3. The Cu/(In+Ga) ratio was 1.03, the Ga/(In+Ga) ratio was 0.16.
The ink was prepared by milling of the oxides mixture, a dispersing agent (Orotan 1124) and water. The ink was coated on the stainless steel to form the oxides film. The results indicated that the aggregation of nanoparticles was the major factor in the unstableness of the ink. The stabilization of the ink can be improved by reducing the size of the particle and enhancing electrostatic force of nanoparticles.
After it was annealed in air, the oxides film was reduced in H2 gas in order to form Cu-In-Ga (CIG) alloys film. The results revealed that the temperature of reduction was the most important effects on the morphology and composition of alloys film. When the temperature was higher than 550℃, there appeared many spherical particles on the alloys film. The optimal conditions of reduction were that the temperature was 500℃and the time was 60 minutes. The alloys consisted of Cu11In9, Cu9In4, In2O3 and Cu. The Cu/(In+Ga) ratio was 0.98, the Ga/(In+Ga) ratio was 0.16.
The CIGS film was obtained by the selenizing of Cu-In-Ga alloys using solid Se as raw materials in vacuum. The optimal conditions of selenization were that the first stage was at 250℃for 30 minutes, the second stage was at 550℃for 40 minutes. The XRD and EDS results showed that the production was polycrystalline CuIn1-xGaxSe2. The Cu/(In+Ga) ratio was 0.92, the Ga/(In+Ga) ratio was 0.14, the Se/(Cu+In+Ga) ratio was 0.92.
The reslut of hall effect measurement showed that the CIGS film was p-type semiconductor. The carrier concentration, mobility and the resistivity of CIGS film were about 4.5×1014/cm3, 217cm2/V·s and 63Ω·cm, respectively. The spectrum analysis indicated that the band-gap of the CIGS film was higher than 1.1eV, which can be used in the solar cells.
引文
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